Catalytically cracked gasoline currently forms a major part of the gasoline product pool in the United States and it provides a large proportion of the sulfur in the gasoline. The sulfur impurities may require removal, usually by hydrotreating, in order to comply with product specifications or to ensure compliance with environmental regulations, both of which are expected to become more stringent in the future, possibly permitting no more than about 300 ppmw sulfur in motor gasolines; low sulfur levels result in reduced emissions of CO, NOx and hydrocarbons.
Naphthas and other light fractions such as heavy cracked gasoline may be hydrotreated by passing the feed over a hydrotreating catalyst at elevated temperature and somewhat elevated pressure in a hydrogen atmosphere. One suitable family of catalysts which has been widely used for this service is a combination of a Group VIII and a Group VI element, such as cobalt and molybdenum, on a substrate such as alumina. After the hydrotreating operation is complete, the product may be fractionated, or simply flashed, to release the hydrogen sulfide and collect the now sweetened gasoline.
Cracked naphtha, as it comes from the catalytic cracker and without any further treatments, such as purifying operations, has a relatively high octane number as a result of the presence of olefinic components. In some cases, this fraction may contribute as much as up to half the gasoline in the refinery pool, together with a significant contribution to product octane.
Hydrotreating of any of the sulfur containing fractions which boil in the gasoline boiling range causes a reduction in the olefin content, and consequently a reduction in the octane number and as the degree of desulfurization increases, the octane number of the normally liquid gasoline boiling range product decreases. Some of the hydrogen may also cause some hydrocracking as well as olefin saturation, depending on the conditions of the hydrotreating operation.
Various proposals have been made for removing sulfur while retaining the more desirable olefins. The sulfur impurities tend to concentrate in the heavy fraction of the gasoline, as noted in U.S. Pat. No. 3,957,625 (Orkin) which proposes a method of removing the sulfur by hydrodesulfurization of the heavy fraction of the catalytically cracked gasoline so as to retain the octane contribution from the olefins which are found mainly in the lighter fraction. In one type of conventional, commercial operation, the heavy gasoline fraction is treated in this way. As an alternative, the selectivity for hydrodesulfurization relative to olefin saturation may be shifted by suitable catalyst selection, for example, by the use of a magnesium oxide support instead of the more conventional alumina.
U.S. Pat. No. 4,049,542 (Gibson) discloses a process in which a copper catalyst is used to desulfurize an olefinic hydrocarbon feed such as catalytically cracked light naphtha. This catalyst is stated to promote desulfurization while retaining the olefins and their contribution to product octane.
In any case, regardless of the mechanism by which it happens, the decrease in octane which takes place as a consequence of sulfur removal by hydrotreating creates a tension between the growing need to produce gasoline fuels with higher octane number and—because of current ecological considerations—the need to produce cleaner burning, less polluting fuels, especially low sulfur fuels. This inherent tension is yet more marked in the current supply situation for low sulfur, sweet crudes.
Processes for improving the octane rating of catalytically cracked gasolines have been proposed. U.S. Pat. No. 3,759,821 (Brennan) discloses a process for upgrading catalytically cracked gasoline by fractionating it into a heavier and a lighter fraction and treating the heavier fraction over a ZSM-5 catalyst, after which the treated fraction is blended back into the lighter fraction. Another process in which the cracked gasoline is fractionated prior to treatment is described in U.S. Pat. No. 4,062,762 (Howard) which discloses a process for desulfurizing naphtha by fractionating the naphtha into three fractions each of which is desulfurized by a different procedure, after which the fractions are recombined.
The octane rating of the gasoline pool may be increased by other methods, of which reforming is one of the most common. Light and full range naphthas can contribute substantial volume to the gasoline pool, but they do not generally contribute significantly to higher octane values without reforming. They may, however, be subjected to catalytically reforming so as to increase their octane numbers by converting at least a portion of the paraffins and cycloparaffins in them to aromatics. Fractions to be fed to catalytic reforming, for example, with a platinum type catalyst, need to be desulfurized before reforming because reforming catalysts are generally not sulfur tolerant; they are usually pretreated by hydrotreating to reduce their sulfur content before reforming. The octane rating of reformate may be increased further by processes such as those described in U.S. Pat. No. 3,767,568 and U.S. Pat. No. 3,729,409 (Chen) in which the reformate octane is increased by treatment of the reformate with ZSM-5.
Aromatics are generally the source of high octane number, particularly very high research octane numbers and are therefore desirable components of the gasoline pool. They have, however, been the subject of severe limitations as a gasoline component because of possible adverse effects on the ecology, particularly with reference to benzene. It has therefore become desirable, as far as is feasible, to create a gasoline pool in which the higher octanes are contributed by the olefinic and branched chain paraffinic components, rather than the aromatic components. Environmental regulations related to motor fuels have produced substantial changes in refinery operations. To comply with these regulations, some refineries have excluded the C6 compounds from the reformer feed to satisfy the low-level benzene requirement. A new refinery process able to alkylate benzene and sulfur compounds with the olefins contained in the same gasoline stream would be beneficial not only to meet benzene specification but also to comply with sulfur regulations.
A series of patents originating from Mobil Oil Corp. describe a process for the upgrading of gasoline by sequential hydrotreating and selective cracking steps. In the first step of the process, the naphtha is desulfurized by hydrotreating and during this step some loss of octane results from the saturation of olefins. The octane loss is restored in the second step by a shape-selective cracking, preferably carried out in the presence of an intermediate pore size zeolite such as ZSM-5. The product is a low-sulfur gasoline of good octane rating. The patents in this series are typified by the first, U.S. Pat. No. 5,346,609. Developments of the basic process with alternative methods of sulfur removal intended to further minimize octane loss are U.S. Pat. No. 5,318,690, in which the naphtha is split into two fractions with the light fraction subjected to an extractive sulfur removal operation which preserves olefin content the heavy fraction which contains relatively fewer of the desirable high-octane olefins is desulfurized by hydrodesulfurization and any resulting octane loss is restored by a selective cracking over a zeolite. A further development described in U.S. Pat. No. 5,360,532 uses a final extraction step to remove recombinant mercaptans. When this process is applied to heavy catalytic naphtha (HCN), the yield loss can be between 6 to 15% while maintaining a similar octane value. The yield loss is highly dependent on octane-recovered value and the type of feed. Heavy catalytic naphtha is the ideal stream for this technology as higher losses are obtained with full range or intermediate catalytic naphthas.
A different approach was taken to sulfur removal by Exxon Research and Engineering Company in the selective naphtha hydrofining process described in various patents including: U.S. Pat. No. 5,985,136; U.S. Pat. No. 6,126,184; U.S. Pat. No. 6,231,753; 6,409,913; U.S. Pat. No. 6,231,754; U.S. Pat. No. 6,013,598; U.S. Pat. No. 6,387,249; U.S. Pat. No. 6,596,157. The ExxonMobil selective naphtha naphtha hydrofining process, SCANfining™, which incorporates aspects of the processes described in these patents, which is commercially available under license from ExxonMobil Research and Engineering Company has demonstrated itself to be a very effective naphtha desulfurization process. This selective naphtha hydrofining process was developed for deep hydrodesulfurization with maximum preservation of the olefins (octane). The single stage version of the process can be used with a full range catalytic naphtha or with an intermediate catalytic naphtha (ICN), for example a nominal 65-175° C. (150-350° F.) or a heavy catalytic naphtha (HCN), for example, a nominal 175° C.+ (350° F.+) naphtha, or both. The two-stage version of the process, as described in U.S. Pat. No. 6,231,753, WO 03/048273 and WO 03/099963, adds a second reactor and inter-stage removal of H2S allowing very deep HDS with very good olefin retention. The operation of this process relies on a combination of a highly selective catalyst with process conditions designed to achieve hydrodesulfurization with minimum olefin saturation.
In cases where the sulfur content of the naphtha is modest and very deep HDS is not required, the SCANfining process can be an attractive option. If severe HDS conditions are needed, it is generally better to treat the LCN stream separately to preserve the maximum amount of olefins. Co-pending application U.S. Ser. No. 11/898,675, claiming priority from U.S. Ser. No. 60/852,404, filed 18 Oct. 2006, entitled “Process for selective sulfur removal from FCC naphthas using zeolite catalysts”, describes a process in which the cracked naphtha feed is subjected to selective hydrofining to remove sulfur without sacrificing octane (hydrodesulfurization typically around 85%) followed by a downstream alkylation a solid, acidic molecular sieve catalyst under mild conditions to shift sulfur species from the lighter, olefin-rich portions of the naphtha to the heavy, olefin-poor gasoline.